Compounds and preparation thereof

ABSTRACT

1. A QUATERNARY AMMONIUM SALT OF THE FORMULA   A-(PHENYLENE(-Q1))-N(-R7)-CO-(LOWER ALKYLENE)-   N(+)(-R1)(-R2)-(LOWER ALKYLENE)-N(-Y)-R0 AN(-)   WHEREIN: A IS NITRO OR AMINO; Q1 IS HYDRGEN, LOWER-ALKYL, LOWER-ALKOXY OR HALOGEN; R0 IS HYDROGEN, LOWER-ALKYL OR HYDROXY-LOWER-ALKYL; R1 IS LOWER-ALKYL, LOWER-ALKENYL OR HYDROXY-LOWER-ALKYL; R2 IS LOWER-ALKYL, LOWER-ALKENYL, HYDROXY-LOWER-ALKYL OR(LOWER-ALKYLENE)-NR0Y; OR R1 AND R2 TOGETHER WITH THE NITROGEN ATOM ARE PYRROLIDINO, PIPERIDINO OR 4-LOWER-ALKANOYL PIPERAZINO; R7 IS HYDROGEN OR LOWER-ALKYL; Y IS HYDROGEN OR   -CO-R   WHEREIN R IS HYDROGEN, LOWER-ALKYL, LOWER-ALKENYL, PHENYL OR PHENYL-LOWER-ALKYL; AND AND IS AN ANION SELECTED FROM THE CLASS CONSISTING OF HALIDES, HYDROXIDES, ALKANOATES, NITRATE, PHOSPHATE, ALKYLSULFONATES AND ARYLSULFONATES.

United States Patent US. Cl. 260501.15 2 Claims ABSTRACT OF THEDISCLOSURE Water-soluble quaternary ammonium dyestuffs useful forcoloring natural fibers, synthetic fiber-forming materials andcellulosic materials in shades of blue and turquoise are obtained by theinteraction of N-(carboxylicacylamino-lower-alkyl) tertiary amines witha phthalocyanine residue bearing from one to five halogenomethyl groups;and water-soluble reds, oranges and yellows are obtained by diazoniumcouplings between dyestuff residues and quaternary ammonium halides inwhich three of the substituents attached to the quaternary nitrogen atomare selected from the group consisting of lower-alkyl, lower-alkenyl,hydroxy-lower-alkyl and N-(carboxylicacylamino-lower-alkyl) and, thefourth substituent either furnishes the diazotizable amino group orserves as the coupling agent. Removal of the acyl group in the N-(carboxylic-acylamino-lower-alkyl)substituent by hydrolysis producesadditional dyestuffs having enhanced substantivity and shades close tothose of their carboxylic-acylamino precursors.

This application is a continuation-in-part of our prior copendingapplication Ser. No. 777,884, filed Nov. 21, 1968, and now abandoned,which in turn is a continuationin-part of our now-abandoned applicationSer. No. 551,- 868, filed May 23, 1 966. 7

This invention relates to cationic dyestuffs. More particularly, thepresent invention relates to novel watersoluble quaternary ammoniumdyestuffs useful in the dyeing art, particularly for coloring naturalfibers, synthetic fiber-forming material and cellulosic materials suchas threads, sheets, fibers, filaments, textile fabrics and the like, aswell as in the manufacture of paper, varnishes, inks, coatings, andplastics.

The dyestuffs of the instant invention are of the formula kAn Formula Iand of the formula ALE it a Formula Ia where in Formula I R is hydrogen,loWer-alkyl or bydroxy-lower-alkyl; R is lower-alkyl, lower-alkenyl orhydroxy-lower-alkyl; R is lower-alkyl, lower-alkenyl,hydroxy-lower-alkyl or -(loweralkylene)-NRY or R and R together with thenitrogen atom, are pyrrolidine, piperidine or 4-lower-a1kanoylpiperazine; Y is hydrogen or 0 ALB wherein R is hydrogen, lower-alkyl,lower-alkenyl, phenyl or phenyl-lower-alkyl; An is an anion; A is amember selected from the group consisting of (1) a phthalocyaninedyestuff residue attached to the quaternary ammonium nitrogen atomthrough a methylene bridge or (2) an aromatic azo dyestuif residueattached to the quaternary ammonium nitrogenatom through alower-alkylene bridge; and k is a small integer whose value is dependenton the nature of A such that it has a range from one to two when A is(2) an aromatic azo dyestufr residue as described above and a range fromone to five when A is (l) a phthalocyanine residue as described above.

In Formula Ia, R is lower-alkyl, lower-alkenyl or hydroxy-lower-alkyl; Ris lower-alkyl or hydroxy-loweralkyl; R is lower-alkyl or lower-alkenyl;A is an aromatic azo dyestuff residue attached to the quaternaryammonium nitrogen atom through a lower-alkylene bridge; and g is a smallinteger Whose value is dependent on the nature of A such that it has arange from one to two.

The terms lower-alkyl, lower-alkenyl, and loweralkylene have the samerespective meanings as hereinafter given.

(1) THE PHTHALOCYANINE DYESTUFFS In the first of its composition ofmatter aspects, the invention sought to be patented resides in theconcept of the novel water-soluble quaternary ammonium phthalocyaninecompounds having the formula Formula II wherein m is an integer from oneto five, n is an integer from zero to two, and p is an integer from zeroto four, wherein m+n+p does not exceed 5; Pc is a phthalocyanineresidue; Q is hydroxy, lower-alkoxy, hydroxy-loweralkoxy, phenoxy, aminoor hydrazine; R" is hydrogen, lower-alkyl or hydroxy-loWer-alkyl; R islower-alkyl, lower alkenyl or hydroxy-lower-alkyl; R is lower-alkyl,lower-alkenyl, hydroxy-lower-alkyl or -(lower-alkylene)- NRY or R and Rtogether with the nitrogen atom are pyrrolidino, piperidine or4-lower-alkanoyl piperazino; Y.

is hydrogen or 0 II -C'-R R COR 1 F l Pc l CHaIII-(l0wer-a1kylene)-N\mm- L R R0 FORMULA III wherein Pc is a phthalocyanine residue, m is aninteger of from one to five, and An, R, R, R and R each have the samerespective meanings indicated in relation to Formula II.

As used throughout, the term lower-alkyl" is a saturated straightorbranched-chain aliphatic radical of from one to six carbon atoms.Lower-alkyl radicals are represented by, for example, methyl, ethyl,propyl, isopropyl, butyl, tert.-butyl, isobutyl, amyl, isoamyl, hexyland the like.

As used herein, the term An represents Anion. By Anion is meant anymonovalent ion derived from an organic or inorganic acid, H Anion, bythe removal of an acidic hydrogen ion. Exemplary anions are, halide,hydroxy, alkanoate, nitrate, phosphate, alkylsulfonate andarylsulfonate. Other monovalent anions are found in the literature forexample, Hackhs Chemical Dictionary, 3rd Edition (1946), at pages 12-13,and Chemical Abstracts, vol. 56, Nomenclature, at pages 72n-80n, bothincorporated herein by specific reference thereto. As is known, oneanion can be changed to another anion by use of conventional ionexchange methods. The halides, i.e. chloride, bromide, fluoride andiodide and in particular chloride and bromide are particularly preferredas the anion for the dyestuffs of this invention because of thegenerally ready availability of the quaternizing agents containing them.However, the scope of the compounds herein described and claimed is inno way to be thereto restricted.

As used throughout, the term lower-alkoxy means an alkoxy radical inwhich the aliphatic portion is-a saturated straightor branched-chain offrom one to four carbon atoms. Lower-alkoxy radicals are presented by,for example, methoxy, ethoxy, propoxy, butoxy, isopropoxy, tert.-butoxyand the like.

As used throughout, the term lower-alkenyl" is a straightorbranched-chain aliphatic radical of from two to six carbon atomscontaining at least one carbon-tocarbon double bond. Lower-alkenylradicals are represented by, for example, vinyl, allyl, methallyl,2-butenyl, 2,4-pentadienyl, 3-hexenyl, and the like.

As used throughout, the term (lower-alkylene) means a divalent,saturated straightor branched-chain aliphatic radical of from two to sixcarbon atoms having valence bonds attached to different carbon atoms.Thus, radicals represented by the term (lower-alkylene) are, forexample, CHzCH2,

and the like.

The benzene ring of phenyl can bear substituents of the kind commonlyemployed in the phthalocyanine art. The presence of such substituentsdoes not ordinarily affect adversely the properties of the resultingdyestuffs, and such substituted compositions are the full equivalents ofthe compositions claimed herein.

As used throughout, the term carboxylic-acyl" is a radical derived bythe removal of the hydroxy radical from a carboxylic acid. Thecarboxylic-acyl groups,

(shown alternatively herein as COR) are represented by lower-alkanoyl,wherein R is lower-alkyl; loweralkenoyl, wherein R is lower-alkenyl;benzoyl, wherein R is phenyl, which may be substituted on the benzenering thereof without deleterious effects; and phenyl-lower alkanoyl,wherein R is phenyl-lower-alkyl. Examples of carboxylic-acyl groupsinclude, for example, formyl, acetyl, propionyl, isobutyryl, acrylyl,methacrylyl, benzoyl, p-toluoyl, p-nitrobenzoyl, o-chlorobenzoyl,phthaloyl, phenylacetyl, p-methoxyphenylacetyl, and the like.

The term Pc, defined as a phthalocyanine residue, represents aphthalocyanine from which m hydrogen atoms have been removed. The termphthalocyanine is used herein in the generic sense to mean the class oftetraazaporphins in which each of four pyrrole nuclei is fused to anaromatic nucleus, e.g. that of benzene. Phthalocyanine itself(tetrabenzotetraazaporphin) is a well-known example of the class, butthe usefulness of this invention is not limited thereto. Moreover, thephthalocyanine residue, Pc, can be metal-free, or it can contain a metalin complex combination, for example, copper, cobalt, nickel, iron, zincand the like. In addition the phthalocyanine residue can be substitutedwith substituents known in the art to modify the shade and otherphysical characteristics of the phthalocyanines in general. Examples ofsuch substituents include chloro, bromo, sulfonic acid, phenyl, benzoyland methyl.

The halogenomethyl group in the starting material is represented by -CHF, CH Cl, CH Br and -CH I. Because they are much cheaper to prepare, weprefer to use as the starting material chloromethyl-substitutedphthalocyanines which are conveniently prepared by methods known to theart.

As used throughout, the term halogen includes bromine, chlorine, iodineand fluorine.

A preferred embodiment in accordance with the phthalocyanine compositionaspect of this invention comprises the highly water-solublephthalocyanine dyestuffs, characterized by the presence in the moleculeof from one to five N-(amino-lower-alkyl) quaternary ammonium radicalsin which the quaternary ammonium nitrogen atoms are each attached to aphthalocyanine radical through a methylene bridge. These dyestuffs arepreferred because of their high substantivity to various fibers and inparticular to cellulosic materials. This embodiment of the invention isillustrated graphically by Formula IV I R H I |:Pc CH -N Goweralkylene)-N mAnl I m Formula IV R3 GHQ-CH: [P0] CHz N NCOR] mAn 2- z inFormula V wherein Pc, R, m, and An are each as defined above and R is amember of the class consisting of lower-alkyl, hydroxy-lower-alkyl, andphenyl-lower-alkyl.

Still another particular embodiment in accordance with thephthalocyanine composition aspect of this invention comprises valuableand highly water-soluble dyestuffs obtained by removing thecarboxylic-acyl group, COR, from the dyestuffs of Formula V. Thephthalocyanine dyestuffs produced according to this embodiment of theinvention are characterized by the presence in the molecule of from oneto five piperazinium radicals, and are illustrated graphically byFormula VI R3\ /CH3-CH1 [Po] CH2N\ \NH] mAn- L CHrin Formula. VI whereinPc, R m and An are as defined above. The dyestuffs of this embodiment ofthe invention are conveniently prepared by hydrolysis of the4-(carboxylicacyl)piperazinium dyestuffs illustrated by Formula V byheating said compounds in dilute aqueous alkali, or preferably in diluteaqueous mineral acid, for example dilute hydrochloric acid as describedhereinbelow.

In the first of its process aspects, the invention sought to be patentedresides in the concept of the process which comprises heating ahalogenomethyl-substituted phthalo cyanine, Le, a phthalocyanine hearingfrom one to five halogenomethyl substituents, with a compound of theFormula N- (lower-alkylene)l l C O R wherein R, R R and R have the samerespective meanings given hereinbefore, in a suitable medium, forexample a polar solvent. Quaternization is usually complete in from twoto forty-eight hours, depending upon the nature of the reactants, thenature of reaction medium, and the reaction temperature. The reactiongenerally proceeds readily at temperatures in the range 50110' C. It isconvenient to employ a reaction medium which boils within the specifiedrange in order that the reaction temperature is maintained by merelyrefluxing the medium. Convenient media for carrying out the processaccording to this aspect of the invention include water; the loweralcohols, for example, methanol, ethanol, isopropyl alcohol, and thelike; the lower-alkylene glycols, for example, ethylene glycol andpropylene glycol; acetonitrile; and dimethylformamide. We generallyprefer to use water or isopropyl alcohol as the reaction media becausethey have suitable boiling points and are inexpensive.

The starting materials for preparing the compounds of Formula III areknown classes of compounds, the methods of preparation of which aredescribed in the prior art. For example, thepoly(halogenomethyl)phthalocyanines are prepared by causingphthalocyanines to react with formaldehyde and a hydrogen halide oralternatively from phthalocyanines and bis(halomethyl) ether. Thecarboxylic-acylamino-lower-alkylamines are prepared by acylatingalkylenediamines in which one of the nitrogen atoms is disubstituted andthe other is either unsubstituted or monosubstituted. The reaction iscarried out according to conventional procedures by causing the aminefunction (bearing at least one hydrogen atom) of an alkylenediamine, R RN-lower-alkylene-NHR to react with an acylating agent, for example, acarboxylic acid, carboxylic acid anhydride, carboxylic acid ester, or acarboxylic acid halide. Examples of such acylating agents include'formicacid, acetic anhydride, phthalic anhydride, methyl benzoate, benzoylchloride, and the like.

The dyestuffs of the embodiment of the invention illustrated by FormulaIV are prepared by removing the carboxylic acyl groups, -COR, from thedyestucs of Formula III which contain from one to fivecarboxylicacylamino-lower-akyl-quaternary ammonium halide radicals eachbonded to the phthalocyanine group through a methylene bridge, asdescribed above. The removal of the carboxylic acyl groups isconveniently accomplished through hydrolysis by heating the acylaminodyestuffs in admixture with dilute aqueous acid. We generally prefer toprepare the quaternary ammonium dyestuffs in the form of the chloridesalt because the chlorides are inexpensive; therefore, we prefer tohydrolyze the acylamine groups with dilute hydrochloric acid in order toprevent introduction of extraneous anion contaminants. However, thehydrolysis is effectively accomplished by any of the common dilutemineral acids, for example, hydrochloric acid, hydrobromic acid,hydriodic acid, sulfuric acid, phosphoric acid, and the like, as well asby aqueous strong organic acids, for example p-toluene-sulfonic acid,benzenesulfonic acid, and the like. Moreover, inasmuch ascarboxylic-acylamides are known to be hydrolyzed by aqueous alkali, suchmay also be used for the hydrolysis herein, but with concomitantintroduction of the hydoxide ion as an anion contaminant.

The dyestuffs prepared according to the embodiments of the inventionillustrated by Formula IV and Formula VI, each contain a basic aminogroup in addition to the quaternary ammonium group which characterizesall of the dyestuffs of our invention. It is obvious that the saidphthalocyanine amino-basic dyestuffs can exist either in free base formor in acid-addition salt form. For the purpose of our invention, the twoforms are full equivalents, because the dyestuffs are water-soluble ineither form, and salt formation is believed not to affect the physicalproperties of the dyestuffs either adversely or beneficially.

The dyestuffs of the embodiment of the invention illustrated by FormulaV are prepared by reacting a poly (halogenomethyl)phthalocyanine with a4-carboxylicacylated piperazine of the formula wherein R and R aredefined above. The reaction conditions for the preparation of dyestuffsaccording to this aspect of our invention are in all respects the sameas those for the preparation of compounds of Formula III.

The acylated piperazine starting material is prepared by theconventional acylation of the appropriate monosubstituted piperazine,for example, N-methylpiperazine, N-ethylpiperazine,N-(Z-hydroxyethyl)piperazine, N-benzylpiperazine,N-(chlorobenzyl)piperazine, and the like. In the preparation of theacylated amine reactants herein which also contain a hydroxyl group, theamine may be preferentially acylated by known methods, or the hydroxylgroup as well as the amine group may be acylated and, if desired, theacyl group may be removed by hydrolysis after the formation of thewater-soluble phthalocyanine dyestuffs described herein.

Although the dyestuffs obtained in accordance with the phthalocyaninecomposition and process aspects of the invention include especiallythose compositions depicted generically by Formulas III, IV, V and VI,it is possible, and indeed probable, that the preparative reaction leadto the formation of products containing functional groups, Q, resultingfrom the reaction of halogenomethyl groups with the solvent,particularly when the solvent is water or an alcohol. For example, whenisopropyl alcohol is employed as the reaction medium, the formation ofproducts containing one or more isopropoxymethyl moieties is likely.Similarly, when water is employed as the reaction medium, it is likelythat products having one or more hydroxymethyl moieties will be formed.We also envisage the intentional incorporation of said substituents, forexample, hydroxy, amino, hydrazino, hydroxy-lower-alkoxy, and phenoxymoieties in the dyestuffs in order to vary slightly the physicalproperties, for example, the shade and solubility, thereof. Suchincorporation is easily accomplished by adding quantities of water,amines, hydrazines, lower alcohols, or phenols as reactants to themixture before quaternization is complete. Compounds containing suchgroups in addition to the quaternary-ammonium functional groups whichcharacterize our dyestuffs are within the scope of our invention.

(2) QUATERNARY AMMONIUM AZO DYEST UFF S In a second composition ofmatter aspect, the invention sought to be patented resides in theconcept of the novel water-soluble quaternary ammonium azo compoundshaving the formula Formula VII wherein c is in integer from one to two;R is hydrogen, lower-alkyl or hydroxy-lower-alkyl; R is lower-al'kyl,

lower-alkenyl or hydroxy-lower-alkyl; R is lower-alkyl, lower-alkenyl,hydroxy-lower-alkyl or -(lower-a1kylene) NRY or R and R together withthe nitrogen atom, are pyrrolidino, piperidino or 4-loWer-alkanoylpiperazino; Y is hydrogen or wherein R is hydrogen, lower-alkyl,lower-alkenyl, phenyl or phenyl-lower-alkyl; An is an anion; Y is adivalent moiety of the formula in which Q is hydrogen, lower-alkyl,loWer-alkoxy or halogen and R is hydrogen or lower-alkyl; and Z is aradical derived from the group of coupling components consisting of CH3CH3 in which Q Q and Q are each hydrogen, lower-alkyl, lower-alkoxy,hydroxy, nitro, amino, carbo-lower-alkoxy, carboxamido, sulphamyl orhalogen; Q and Q are each hydrogen, lower alkyl, lower-alkoxy orhalogen; Q is hydrogen, lower-alkyl, lower-alkoxy, nitro or halogen; Ris lower-alkyl, lower-alkoxy, carboxamido or carbo-loweralkoxy; R ishydrogen, lower-alkyl, halogen, benzoxazol- 2-yl or benzimidazol-Z-yl; Ris hydrogen, lower-alkyl or halogen; and Y is 1,4-phenylene or1,2-ethylene.

novel water-soluble quaternary ammonium azo compounds having the formulaN-(lower alkylene)-N c An Formula VIII wherein c is an integer from oneto two; R is hydrogen, lower-alkyl or hydroxy-lower-alkyl; R islower-alkyl, lower-alkenyl or hydroxy-lower-alky1; R is lower-alkyl,lower-alkenyl, hydroxy-lower-alkyl or -(lower-alkylene)- NRY or R and Rtogether with the nitrogen atom are pyrrolidino, piperidino or4-lower-alkanoyl piperazino; Y is hydrogen or i -OR wherein R ishydrogen, lower-alkyl, lower-alkenyl, phenyl or phenyl-lower-alkyl; Anis an anion; Y is a divalent moiety of the formula in which the freevalence attached to the ring system is bonded to the azo group, and R"is hydrogen or loweralkyl; and T is either a monovalent residue selectedfrom the group consisting of Q, Q Q Q when 0 is one or a divalentresidue from the group consisting of SO H so,H

when 0 is two in which Q and Q are each hydrogen, lower-alkyl,loweralkoxy or halogen,( Q and Q are each hydrogen, lower- Formula IXwherein c is an integer from one to two; R is loweralkyl, lower-alkenylor hydroxy-lower-alkyl; R is loweralkyl or hydroxy-lower-alkyl; R islower-alkyl or loweralkenyl; An is an anion; Y is a divalent moiety ofthe formula Q1 in which Q is hydrogen, lower-alkyl, lower-alkoxy orhalogen; and Z is a radical derived from the group of couplingcomponents consisting of H II in which Q Q and Q are each hydrogen,lower-alkyl, lower-alkoxy, hydroxy, nitro, amino, carbo-lower-alkoxy,carboxamido, sulphamyl or halogen; Q and Q are each hydrogen,lower-alkyl, lower-alkoxy or halogen; Q is hyconcept of the processwhich comprises diazotizing an amine of the formula R Y H2N-Y-(1ower-allq lene) I I-(lower-allrylene) -N R An R Formula X wherein An,R R R Y and Y are as defined above in relation to Formula VII, andcoupling approximately 0 molecular proportion of the diazonium salt withone molecular proportion of a coupling component, Z, which has the samemeanings given hereinabove in relation to Formula VII.

In a third process aspect, the invention sought to be patented inrelation to the water-soluble quaternary ammonium azo compounds ofFormula VIII, resides in the concept of the process which comprisescoupling approximately 0 molecular proportions of a compound of theformula R Y H-W-(lower-alkylene) 1-I I-(lower-alkylene) -N R An R 0Formula XI wherein Anfi R R R Y and Y are as defined above in relationto Formula VIII, with one molecular porportion of the diazonium saltobtained by diazotization of an amine having the formula wherein c and Thave the same meanings given hereinbefore in relation to Formula VIII.

In a fourth process aspect, the invention sought to be patented inrelation to the water-soluble quaternary azo compounds of Formula IX,resides in the concept of the process which comprises diazotizing anamine of the formula RB HzNT -(lower-alkylene) I T- R I l" An FormulaXII wherein Y R R R and An are as defined above in relation to FormulaIX, and coupling approximately c molecular proportion of the diazoniumsalt with one molecular proportion of a coupling component, Z which hasthe same meanings given hereinabove in relation to Formula IX.

In the preparation of the compounds of Formula VII, and of Formula IXand the ratio of the quantity of diazonium compound to couplingcomponent is, of course, dependent on the number of coupling sitesavailable in the coupling component. Thus when a single coupling site ispresent, for example in a 1-phenyl-2-pyrazolin-5- one, there is employedapproximately one molecular proportion of the diazoniuum compound andwhen two coupling sites are available as, for example, in4,4'-bi-oacetoacetotoluidide (Naphthol AS-G), there are employedapproximately two molecular proportions of the diazonium compound. Inthe preparation of those compounds of Formula VIII wherein two azolinkages are present, there is employed approximately one-half molecularproportion of the tetrazonium compound for reaction with approximatelyone molecular proportion of the quaternary ammonium coupling component.Since the reaction temperature has some effect on the shade of theresulting water-soluble quaternary ammonium dyestuffs, it is ordinarilydesirable to maintain adequate control of the temperature of thereaction mixture in some predetermined manner. It is generallysatisfactory to stir the reactants together at a temperature in theapproximate range 035 C. to effect only an incomplete coupling reaction,and then heat the mixture at a higher temperature, for instance in theapproximate range 40-60" C., preferably at 50-55 C., to complete thecoupling reaction and develop the dyestulf. The reaction is begun in analkaline aqueous medium but the pH of the reaction mixture drops duringthe process to a final value of about 5.0.

In a fifth process aspect, the invention sought to be patented inrelation to the preparation of water-soluble quaternary ammonium azocompounds of Formula VII and of Formula VIII wherein Y is hydrogen,resides in the concept of the process which comprises hydrolyzing acompound of Formula VII or of Formula VIII wherein Y is COR in which Ris as defined above. As stated hereinbefore in the case of thephthalocyanine dyestuffs of our invention, the removal of the carboxylicacyl groups is conveniently accomplished through hydrolysis by heatingthe acylamino dyestuffs in admixture with dilute aqueous acid. Althoughthe hydrolysis is effectively accomplished by the use of any of thecommon dilute mineral acids as well as by aqueous strong organic acidsas previously enumerated, we here also prefer to hydrolyze the acylaminegroups with a dilute aqueous acid whose anion is the same as thequaternary anion in order to prevent introduction of extraneous anioncontaminants. Moreover, the carboxylic-acylamides of Formula VII and ofFormula VIII may be hydrolyzed by aqueous alkali, but of course, withconcomitant introduction of the hydroxide ion as an anion contaminant.

Alternatively, the compounds of Formula VII in which Y is hydrogen, canbe prepared by coupling in approximately stoichiometric proportions acoupling component, Z, as defined in relation to Formula VII, with adiazotized amino compound of Formula X in which Y is hydrogen.Similarly, an alternate method for preparing the compounds of FormulaVIII in which Y is hydrogen comprises coupling in approximatelystoichiometric proportions a compound of Formula XI in which Y ishydrogen with a diazonium compound of the formula wherein c, T and Anhave the same meanings as hereinbefore indicated. Although theintermediates of Formula X and XI in which Y is hydrogen can beseparately prepared and isolated for use in preparing the compounds ofFormula VII and Formula VIII in which Y is hydrogen, it is not necessaryto do so. It is particularly convenient to first hydrolyze the acylatedintermediates of Formula X or of Formula XI and to then proceed directlywith the diazotization and coupling in the same reaction vessel.

When preparing the compounds of Formula VII in which Y is hydrogen and Yis by hydrolysis of the corresponding compound of Formula VII in which Yis COR, it is preferred to hydrolyze those compounds in which R ishydrogen or equivalently in which Y is formyl. The formyl group ispreferred because it is readily hydrolyzed with minimal concomitanthydrolysis of the remaining amide group. In the same sense and for thesame reason, it is preferred to employ those compounds of Formula X inwhich Y is formly when Y is R1 Q1 \C for the preparation of thecorresponding intermediates of Formula X in which Y is hydrogen.

The water-soluble quaternary ammonium azo dyestuffs prepared accordingto this aspect of our invention contain one or more primary amino groupsin addition to the quaternary ammonium group which characterizes all ofthe dyestuffs of our invention. The said amino-basic dyestuffs can, ofcourse, exist either in free base form or in acid-addition salt form.For the purpose of our invention, the two forms are full equivalents,because the dyestulfs are water-soluble in ether form, and saltformation is believed not to affect the physical properties of thedyestuffs either adversely or beneficially.

In a fifth composition of matter aspect, the invention sought to bepatented resides in the concept of the N-R N-[(lower alkylene) -Y -NH]-N-R -N-[(lower alkylene)-NRY] ammonium halides, the N-R-N-[(loweralkylene) -Y -H]-N-R -N[ (lower-alkylene -NRY] ammoniumhalides, and the N-R -N[(lower-alkylene)-Y NH ]-N-R -N-R ammoniumhalides represented and defined by Formulas X, XI, XII respectivelywhich are useful intermediates in the preparation of the quaternaryammonium azo dyestuffs of the invention.

The manner and process of making and using the quaternary ammonium azodyestuffs of the invention, and the best mode contemplated by theinventors of carrying out this invention, will now be described so as toenable any person skilled in the art to which it pertains to make anduse the same.

The intermediate N-R -N-[(lower-alkylene) -Y -NH N-R-N-[(lower-alkylene)-NRY] ammoniun halides of Formula X in which Y isCOR, are conveniently prepared in two steps, firstly by heating ahalogeno-loweralkylene-substituted nitrobenzene or ahalogeno-loweralkylene carboxylic acid N-R' -nitroanilide with acompound of the formula R C O R N-lower-alkylene-N wherein R, R R R andR' have the same respective meanings given hereinbefore, in a siutablemedium, for example a polar solvent, to obtain the nitro-substitutedprecursors of the intermediates of Formula X wherein Y is respectively.Quaternization is usually complete in from two to forty-eight hours,depending upon the nature of the reactants, the nature of the reactionmedium, and the reaction temperature. The reaction generally proceedsreadily at temperatures in the range 50-1 10 C. It is convenient toemploy a reaction medium which boils within the specified range in orderthat the reaction temperature is maintained by merely refluxing themedium. Convenient media for carrying out the process according to thisaspect of the invention include water; the lower-alcohols, for examplemethanol, ethanol, ispropyl alcohol, and the like; the lower-alkyleneglycols, for example, ethylene glycol and propylene glycol;acetonitrile; and dimethylformamide. We generally prefer to use isopropyl alcohol or water as the reaction media because they have suitableboiling points and they are inexpensive. The N R N [(lower-alkylene) YNO ]-N-R [(lower-alkylene)NRCOR]ammonium halide thus obtained is then inthe second step subjected to reduction of the nitro group to obtain thecorresponding aminosubstituted intermediates of Formula X in which Y isCOR. Reduction is carried out with powdered iron under essentiallyneutral conditions. The reduction generally proceeds readily in aqueousmedia at a temperature in the range 50-75" C. Alternatively,high-pressure, catalytic reduction is employed. We have found that whenthe latter method is used, reduction is conveniently and efficientlyeffected in aqueous media at approximately E13. 600 pounds per squareinch hydrogen pressure at a temperature between 60-80 C. Although any ofthe known poisoned reduction catalysts may be used, we prefer to use aplatinum sulfide on charcoal catalyst.

The intermediates of Formula X in which Y is hydrogen are obtained bythe hydrolysis of the corresponding compound of Formula X wherein Y isCOR. The hydrolysis is effectively accomplished by heating the acylaminointermediate in admixture with dilute aqueuous acid as hereinbeforedescribed.

Particularly preferred among the novel intermediates of Formula X andtheir corresponding precursors useful for the preparation of thedyestulfs of Formula VII, are those compounds represented by the formulaR Y A I (lower-alkylene) -N-(lwer-a1kyIene)N R an R" and by the formulaR R Y I N-C O-(lower-alkylene) -N-(1ower-alky1ene)-N A 2 rin R where inboth formulas A is nitro or amino; R is hydrogen, lower-alkyl orhydroxy-lower-alkyl; Q is hydrogen, lower-alkyl, lower-alkoxy orhalogen; R is lower-alkyl, lower-alkenyl or hydroxy-lower-alkyl; R islower-alkyl, lower-alkenyl, hydroxy-lower-alkyl or -(lower-alkylene)-NRY or R and R together with the nitrogen atom, are pyrrolidino,piperidino or 4-lower-alkanyl piperazino; Y is hydrogen or o I! CRwherein R is hydrogen, lower-alkyl, lower-alkenyl, phenyl orphenyl-lower-alkyl; An is an anion; and in the latter formula R ishydrogen or lower-alkyl.

The intermediate N-R -N-[(lower-alkylene)-Y -NH N-R -N-R ammoniumhalides of Formula XII are conveniently prepared in two steps, first byheating a halogeno lower-alkylene-substituted nitrobenzene with acompound of the formula wherein R R and R have the same respectivemeanings given hereinbefore without other media or in a suitable medium,for example a polar solvent, to obtain the nitro-substituted precursorsof the intermediate of Formula XII. Quaternization is usually completein from two to forty-eight hours and proceeds readily at temperatures inthe range of 50-110 C. Convenient media for carrying out the processaccording to this aspect of the invention include water; thelower-alcohols, for example, methanol, ethanol, isopropyl alcohol, andthe like; the loweralkylene glycols, for example, ethylene glycol;acetonitrile and dimethyl formamide. We generally prefer to use water asthe reaction medium because it has a suitable boiling point and isinexpensive. The N-R -N-[flower-alkylene)-Y -NO ]-N-R -N-R ammoniumhalide thus obtained is in the second step subjected to reduction of thenitro group to obtain the corresponding amino-substituted intermediatesof Formula XII. Reduction is carried out with powdered iron underessentially neutral conditions. The reduction generally proceeds readilyin aqueous media at a temperature in the range 50-75 C. Alternatively,high-pressure, catalytic reduction of the nitro group is employed inaqueous media at approximately 600 pounds per square inch hydrogenpressure at tem- I Q-(lower-alkyleneN-N-R' A w A13 wherein A is nitro ofamino; Q is hydrogen, lower-alkyl, lower-alkoxy or halogen; R islower-alkyl, lower-alkenyl or hydroxylower-alkyl; R is lower-alkyl orhydroxy-lower-alkyl; R is lower-alkyl or lower-alkenyl; and An is ananion.

The halide quaternizing agents used as starting materials for preparingthe intermediate compounds of Formula X and of Formula XII are agenerally known class of compounds, and are readily prepared by methodswellknown in the art. For example, thehalogeno-lower-alkylene-substituted nitro-benzenes are prepared bynitration of the appropriate halogeno-lower-alkylene-substitute benzeneswhich in turn are prepared by the interaction of the correspondinghydroxy-lower-alkylene-substituted benzene with an hydrogen halide or anhydrogen halideproducing reactant, for example phosphorous oxychloride.Said hydroxy-lower-alkylene-substituted benzenes are likewise agenerally known class of compounds and are prepared by methodswell-known in the art. For example, the Grignard reagent formed from theappropriate aryl halide or the appropriate aralkyl halide is interactedwith formaldehyde or an appropriate alkylene oxide for. introduction ofa hydroxy-alkyl group into the aromatic ring or addition thereof to thealkyl chain. The desired halogeno-lower-alkylene-substitutednitrobenzene isomer is separated by conventional techniques from theresultant mixture of nitrated products or alternatively, said mixturecan be used per se for quaternization with subsequent separation of thedesired quaternary ammonium intermediate. The halogeno-lower-alkylenecarboxylic acid N-R" nitroanilides are prepared, for example, byinteraction of a halogen-substituted alkanoyl halide with an N-R'substituted nitroaniline. The carboxylicacylamino-lower-alky1amines areprepared as hereinbefore described.

The N-R -N-R -N-R amines required for preparing the compounds of FormulaXII are a known class of compounds, the methods of preparation of whichare described in the prior art. For example, the direct alkylation ofprimary and secondary amines with a lower alkyl halide, a lower alkenylhalide or a hydroxy-lower-alkyl halide provides a convenient method forpreparing the requisite tertiary amines.

The N-R -N- lower-alkylene) -Y -I-I] -N-R -N- lower-alkylene)-NRY]ammonium halides of Formula X1 in which Y is -COR, are convenientlyprepared by heating an N-R' -N-(halo-lower-alkylene)-substituted anilinewith a compound of the formula R C O R N -lower-alkylene-N wherein R, RR R and R have the same respective meanings given hereinbefore, toobtain the intermediate of Formula XI wherein Y is The reaction can becarried out without other amide or in a suitable medium for example, apolar solvent. Quaternization is usually complete in form two toforty-eight hours and proceeds readily at temperatures in the range of50-110 C. Convenient media for carrying out the process according tothis aspect of the invention include 15 water; the lower-alcohols, forexample, methanol, ethanol, isopropyl alcohol, and the like; thelower-alkylene glycols, for example, ethylene glycol and propyleneglycol; acetonitrile and dimethylformamide.

Those intermediates represented by Formula XI in which Y is hydrogen areconveniently obtained by the hydrolysis of the corresponding acylaminocompound of Formula XI wherein Y is COR. The hydrolysis is accomplishedby heating the acylamino intermediate in admixture with dilute aqueousacid as hereinbefore described.

Novel intermediates that are particularly preferred and useful for thepreparation of the dyestuffs of Formula VIII and which are within theambit of Formula XI, are those compounds represented by the formula R RY Ari F" in which R is hydrogen, lower-alkyl or hydroxy-loweralkyl; R islower-alkyl, lower-alkenyl or hydroxy-loweralkyl; R is lower-alkyl,lower-alkenyl, hydroxy-loweralkyl or -(lower-alkylene)-NRY or R and Rtogether with the nitrogen atom are pyrolidino, piperidino or 4-lower-alkanoyl piperazino; R is hydrogen or lower-alkyl; Y is hydrogenor wherein R is hydrogen, lower-alkyl, lower-alkenyl, phenyl orphenyl-lower-alkyl; and An is an anion.

The halide quaternizing agents required for preparing the intermediatecompounds of Formula XI are generallyknown classes of compounds and areconveniently prepared by methods well-known in the art. For example, theN-R' -(halo-lower-alkylene)substituted anilines are prepared by causingan N-R' -N-(hydroxy-lower-alkylene)- substituted aniline to react withan hydrogen halide. The carboxylic-acylamino-lower-alkylarnines areprepared as hereinbefore described.

The new water-soluble quaternary ammonium-substituted dyestuffs ofFormulas II, VII, VIII and D( disclosed herein are useful dyestuffswhich can be applied to natural fibers, to fiber-forming syntheticmaterials and to cellulosic materials by methods conventional in thedyeing art since it has been found that the dyestuffs of this inventionare substantive to wool, silk, nylon, rayon, polyacrylonitrile, cottonand paper. The dyed products thus obtained are stable to ultra-violetlight and to washing. The novel dyes are especially valuable forimparting various shades of a stable turquoise, red or yellow color tocotton and to paper, both sized and unsized. For use in the paper trade,our dyes have several outstanding advantages over quaternary ammoniumdyes in the prior art. First, our dyes are less prone to bleed" whenpaper impregnated with the dyes is wet and placed in contact with moistwhite paper. This is a particularly desirable property for dyes designedfor coloring paper to be used in facial tissues, napkins and the like,wherein it can be foreseen that the colored paper, while wet, may comein contact with other surfaces, such as textiles, paper and the like,which should be protected from stain. Another advantageous property ofour new dyes for use in the paper trade is found in their high degree ofcolor discharge when bleached with hypochlorite or "chlorine" bleach.This property of dyes is particularly desired by papermakers in orderthat dyed paper may be completely bleached prior to reprocessing. Stillanother advantageous property of our dyestuffs is found in their highresistance to a change of shade when used to color cellulosic materials,which have either previously been treated with or are treated subsequentto dyeing, with wet-strength resin.

The carboxylic-acylamino compounds and the free amino compounds of theinstant invention are substantially equal with respect to theirbleachability. With respect to shade, in general, the free aminocompounds have slightly deeper shades than the carboxylic acrylaminocompounds. Presumably because of the availability of the free aminegroup to bond with the fiber and Wet-strength resin or similar paperadditives, the free amino compounds are, in general, less prone to bleedthan are the car'boxylic acylamino compounds both when wet with wateralone and in the presence of soap.

Yet another advantage of the dyes of this invention is their property ofbeing absorbed by cellulosic fibers from aqueous solution to a very highdegree and at a very rapid rate. This property is advantageous to thepaper industry, because it allows the dye to be added to the pulp justprior to formation of the sheet.

The structures of the novel compounds herein disclosed Were establishedby the'u mode of synthesis and analysis of their infra-red absorptionspectra, and were corroborated by the correspondence of calculated andfound values of elemental analyses of representative samples.

Our invention is further illustrated by the following procedures andExamples, which are given for the purpose of illustration only, and notto limit the invention thereto. All parts are parts by weight.

PREPARATION OF INTERMEDIATES A. Tetrakis(Chloromethyl) CopperPhthalocyanine Copper phthalocyanine was chlormethylated according toknown procedures by interacting 250 parts of acid pasted copperphthalocyanine with 435 parts of paraformaldehyde and 418 parts ofphosphorus oxychloride in 825 parts of 98 percent sulfuric acid and 1630parts of chlorosulfonic acid. Elemental analysis of the resulting brightblue powder were in excellent agreement with the calculated analysis oftetrakis(chloromethyl)copper phthalocyanine.

B. Carboxylic-Acylamino Lower-Alkylamines The folowing N R N R-N-[(lower-alkylene)- NRCOR1 amines were prepared by interaction of theindicated unsymmetrically disubstituted alkylene diamine and acylatingagent using procedures well-known in the art for acylation.

1. N (3-Dimethylaminopropyl)formamide from 327 parts ofN,N-dimethyl-1,3propanediamine and 180 parts of percent formic acid;

2. N,N-Bis(B-formarnidopropyl)methylamine from 218 parts ofN,N-bsi(3-aminopropyl)methylamine and 203 parts of 90 percent formicacid;

3. N (3-Diethylaminopropyl)formamide from N,N-diethyl-1,3-propanediamine and 90 percent formic acid;

4. N (3-Dimethylaminopropyl)benzamide from 107 parts ofN,N-dimethyl-1,3-propanediamine and 141 parts of benzoyl chloride;

5. N (3-Dimethylaminopropyl)acetamide from N,N-dimethyl-l,3-propanediamine and acetyl chloride;

6. N (4 Diethylamino 1-methylbutyl)formamide fromN,N-diethyl-4-methyl-l,4-diaminobutane and 90 percent formic acid;

7. N-(3-Dimethylaminopropyl)phthalamic acid; from 102 parts ofN,N-dimethyl-1,3-propane diamine and 141 parts of phthalic anhydride;

8. N (3-Diethanolarninopropyl)formamide from N-(3-aminopropyl)diethanolamine and 90 percent formic acid;

9. N [2-(4-Formylpiperazino)ethyl]formamide from2-(4-formylpiparazine)ethylamine and 90 percent formic acid; and

10. N-(Z-Dimethylaminoethyl)formamide from 2-dimethylaminoethylamine and90 percent formic acid.

The following carboxylic-acylamino lower-alkylamines which are withinthe purview of this invention, are prepared using art-known proceduresby acylation of the in- 1 7 dicated unsymmetrically substituted diaminewith the indicated acylating reagent:

N-[Z-(N-Ethyl N 1 methylbutyl)aminoethyl]propionamide from2-(N-ethyl-N-l-methylbutylamino)ethylamine and propionic anhydride;

N (6 Dirnethylaminohexyl)iso-butyramide from 6-(dimethylamino)hexylamine and iso-butyryl chloride;

N-[2 (N-Allyl N ethyl)aminoethyl]p-chlorobenzamide from 2-(N-allyl Nethylamino)ethylamine and pchlorobenzoyl chloride;

N [2 (N Ethyl N methyl)aminoethyl]propionamide from Z-(N-methyl -Nethylamino)ethylamine and propionyl chloride;

N-(2 Piperidinoethyl)acrylamide from 2 piperidinoethylamine and ethylacrylate;

N-[2 (N-n-Butyl N isopropyl)aminoethyl]phenylacetamide from Z-(N-butyl Nisopropylamino)ethylamine and ethyl phenylacetate;

N-(3 Pyrrolidinylpropyl)valeramide from 3 pyrolidinopropylamine andvaleryl chloride;

N-(2 Diallylaminoethyl)phenylpropionamide from 2-(diallylamino)ethylarnine and ethyl phenylpropionate;

N-(2-Diethylaminopentyl) 2 methylacrylamide from5-(diethylamino)pentylamine and methyl methacrylate;

N (2 Diisopropylaminoethyl) p methoxybenzamide from 2(diisopropylamino)ethylamine and p-methoxybenzoylchloride;

N-(2 Diisopentylaminoethyl)butyramide from2-(diisopentylamino)ethylamine and butyryl chloride;

N-(2 Dihexylaminoethyl)n caproamide from 2 dihexylaminoethylamine andcaproyl chloride;

l-Benzyl 4 formyl piperazine from l-benzylpiperazine and formic acid;

N-(6 Diisobutylaminohexyl)acetamide from 6-(diisobutylamino)hexylamineand acetic anhydride;

N-( l-Methyl 3 diethylaminopropyl)acrylamide from3-amino-N,N-diethylaminobutylamine and ethyl acrylate;

l-Ethyl-4-propionyl piperazine from l-ethylpiperazine and propionylchloride;

N-(Z-Di-n-propylamino 2 methylethyl)p-nitrobenzamide from Z-methyl 2 din propylarninoethylamine and ethyl p nitrobenzoate;

N-[3 (N-Methyl N 2 acetamidoethyl)aminopropyl]acetamide fromN-methyl-N-2-aminoethyl 1,3 propanediamine and acetyl chloride;

N-Methyl-N-[2 (N-ethyl N methyl)aminoethyl] propionamide from N-methyl 2(N-methyl-N-ethylamino)ethylamine and propionyl chloride;

N-(3 Hydroxypropyl)-N-(3 dimethylaminopropyl] formamide from N-(3hydroxypropyl)-N,N-dimethyl- 1,3-propanediamine and 90 percent formicacid;

N,N-Bis 3 (N-methylformamido propyl] methylamine from N,N-bis[3(N-methylamino)propyl]methylamine and 90 percent formic acid;

N-Isopropyl N (2 piperidinoethyl)acrylamide from N-isopropyl 2piperidinoethylamine and ethyl acrylate;

N-n-Hexyl N [2 (N-ethyl-N-methyl)aminoethyl] propionarnide fromN-n-hexyl 2 (N-methyl-N-ethylamino)ethylamine and propionic anhydride;

N-Ethyl N (Z-di-n-propylamino 2 methylethyl)pnitrobenzamide from N-ethyl2 methyl-Z-di-n-propylaminoethylamine and ethyl p-nitrobenzoate;

N-(2 Hydroxyethyl) N (4-diethylamino-l-methylbutyl)-formamide fromN'-(2-hydroxyethyl) -N,N-diethyl- 4-methy1-1,4-diaminobutane and 90percent formic acid;

N-n-Butyl N [2 (4 formylpiperazino)ethyl]acetarnide from N-n-butyl 2 (4forrnylpiperazino)ethylamine and acetic anhydride;

N-[3 (NMethylacetamido)propyl]-N-[2 (N-methylacetamido)ethyl]methylaminefrom N [3 (N methylamino)propyl] N [2 (N-methylamino)ethyl]rnethyl amineand acetyl chloride;

N-Methyl N (3 pyrrolidinylpropyl)valeramide from N-methyl 3pyrrolidinylpropylamine and valeryl chloride;

N (2 Diethanolamino 1,1 dimethylethyl)phenylacetamide from 2diethanolamino 1,1 dimethylethylamine and ethyl phenylacetate;

1-(2 Hydroxyethyl) 4 (m-toluoyl)piperazine fromN-(Z-hydroxyethyl)piperazine and methyl m-toluate;

N-[3 (N Isopropyl-N-methyl)aminopropyl]salicylamlde from3-(N-isopropyl-N-methylamino)propylamine and methyl salicylate, and

l-Methallyl 4 valerylpiperazine from l-methallylpiperazine and valerylchloride.

C. N-R -N-[(Lower-alkylene) Y NH N R N [(Lower Alkylene) NRY] QuaternaryAmmonium Intermediates (Formula X) 1. N,N-Dimethyl-N- (3-amino-4-methoxybenzyl -N- 3-formamidopropylammonium chloride.

(a) To a refluxing solution of 35.4 parts ofN-(3-dimethylaminopropyl)formamide in 40 parts of isopropyl alcoholthere was added over a two hour period 50.4 parts of 4-rnethoxy 3nitrobenzyl chloride. Refluxing was continued for four hours after whichthe reaction mixture was diluted with parts of isopropyl alcohol andcooled to 20 C. The solid that separated was collected and washed with asmall amount of fresh isopropyl alco hol and then dried in a vacuum ovento yield 71.1 parts of N,N-dimethyl-N-(3 nitro 4 methoxybenzyl)-N-3-formamidopropylammonim chloride, as a cream colored solid which meltedat ISO-183 C.

(b) A mixture of 30.0 parts of iron powder, 6.0 parts of sodium acetate,and parts of water was heated to 50 C. Heating was stopped and 33.1parts of N,N-dimethyl-N-3-(nitro 4methoxybenzyl)-N-3-formamidopropylammonium chloride was added over aperiod of two and a half hours at a rate such as to maintain thetemperature at 5055 C. At the end of the addition, heating was resumedat 5055 C. for two hours. The reaction mixture was cooled to 25 C. andfiltered with the aid of diatomaceous earth to obtain a pale yellowsolution. A sample of the solution was analyzed for free amine contentby diazotization using a standardized sodium nitrite solution. Theanalytical results indicated that N,N-dimethyl-N-(3 amino 4methoxybenzyl)-N6- formamidopropylammonium chloride was obtained innearly quantitative yield. The product was used directly in the form ofits aqueous solution without isolation.

(c) A mixture of 166 parts of N,N-dimethyl-N-(3- nitro-4-methoxybenzyl)N-3 formamidopropylammoniurn chloride, 200 parts of Water, and 3 partsof a 5 percent platinum sulfide on charcoal mixture was subjected to 600pounds per square inch of hydrogen at 70-75 C. After two and one-thirdhours, when the total up take of hydrogen was approximately 92% oftheory, absorption of hydrogen ceased. The reaction mixture was cooledand filtered with the aid of diatomaceous earth. A sample of thefiltrate was analyzed for free amine content by diazotization using astandardized sodium nitrite solution. The results indicated thatN,N-dimethyl-N-(3-amino-4- methoxybenzyl) N-3-formamidopropylammoniumchloride was obtained in nearly quantitative yield. The product was useddirectly in the form of an aqueous solution without isolation.

2. N,N-Dimethyl-N-(3-amino-4-methoxybenzyl)-N-3- benzamidopropylammoniumchloride (a) Proceeding in a manner similar to that described above inla, and using N-(3-dimethylaminopropyl-benzamide, and3-nitro-4-methoxybenzyl chloride, there was obtained N,N-dimethyl-N-3-nitro-4 methoxybenzyl -N- 3-benzamidopropylammonium chloride, as anoif white solid which melted at 133136 C.

(b) When the N,Ndimethyl-N-(3-nitro-4-methoxybenzyl)-N-3-benzamidopropylammoniumchloride thus obtained is subjected to reduction by either of themethods of lb or 1c above, there is obtained N,N-dimethyl-N-(3- 19amino-4-methoxybenzyl) N-3-benzamidopropylammoniurn chloride.

3. N-Methyl N-(3-amino-4-methoxybenzyl)-N,N-bis(3-formamidopropyl)ammonium chloride (a) A mixture of 54.0 parts ofN,N-bis(3-formamidopropyl)methylamine, 50.4 parts of4-methoxy-3-nitrobenzyl chloride, and 78 parts of acetonitrile wasstirred at reflux for seven and a half hours. An additional 78 parts ofacetonitrile was added to the reaction mixture causing an oil toseparate. Heating at reflux was continued for an additional two hoursand the 140 parts of acetonitrile was distilled away and 200 parts ofwater was added. The remaining acetonitrile was removed by distillationand the cooled reaction mixture was filtered with the aid ofdiatomaceous earth to obtain an aqueous solution ofN-methyl-N-(3-nitro-4-methoxybenzyl)-N,N- bis(3-formamidopropyl)ammoniumchloride. The solution was used directly for reduction of the nitrogroup.

(b) Proceeding in a manner similar to that described above in 1b, andusing 75 parts of iron powder and 15.0 parts of sodium acetate, theN-methyl-N-(3-nitro- 4-methoxybenzyl) N,N-bis(3-formamidopropyl)ammoniumchloride obtained in the form of its aqueous solution from 3a above wasreduced to obtain 61 parts of N- methyl-N-(3-amino-4-methoxybenzyl)N,N-bis(3formamidopropyl)-ammonium chloride in the form of an aqueoussolution.

4. N-Methyl-N- 3-amino-4-methoxybenzy1) -N,N-bis 3-aminopropyl)ammoniurn chloride trihydrochloride N Methyl-N(3-amino-4-methoxybenzyl)-N,N-bis(3- formamidopropyl)ammonium chlorideobtained in 3b above was hydrolyzed by heating in a refluxing solutionof 63 parts of water containing 24 parts of concentrated hydrochloricacid during two hours to obtain N-methyl- N 3 (amino 4 methoxybenzyl)N,N-bis(3-aminopropyl)-ammonium chloride trihydrochloride.

5. N,N-Dimethyl-N-(4-aminophenyl)carbamylmethyl-N-3-formamidopropylammonium chloride (a) In a manner similar to thatdescribed above in 1a, and using 14.2 parts of N-(3-dimethylaminopropyl)formamide, 20.0 parts of 2-chloro-4'-nitroacetanilide, and 78 parts ofisopropyl alcohol there was obtained 27.4 parts ofN,N-dimethyl-N-(4-nitrophenyl)carbamylmethyl-N-3-formamidopropylammonium chloride as a white solid which melted atl95196 C.

(b) Proceeding in a manner similar to that described above in 1b, andusing 68.8 parts of N,N-dimethyl-N- (4-nitrophenyl)carbamylmethyl-N-3formamidopropylammonium chloride obtained above in 3a, 60.0 parts ofiron powder, 12.0 parts of sodium acetate, and 250 parts of water therewas obtained 33.0 parts of N,'N-dimethyl-N-(4-aminophenyl)carbamylmethyl N 3-formamidopropylammonium chloride.

(c) Following the procedure described in lo above,N,N-dimethyl-N-(4-nitrophenyl)carbamylmethyl N 3-formamidopropylammonium chloride was catalytically hydrogenated inaqueous solution at 70-75 C. and at 600 pounds per square inch in thepresence of a 5 percent platinum sulfide on charcoal mixture to obtainN,N- dimethyl N (4-aminophenyl)carbamylmethyl N 3-formamidopropylammonium chloride.

6. N,N-Dimethyl-N-(4-aminophenyl)carbamylmethyl N- 3-aminopropylammoniumchloride hydrochloride A solution of 10.0 parts ofN,N-dimethyl-N-(4-nitrophenyl)carbamylmethyl N 3 formamidopropylammoniumchloride in 100 parts of water containing 6.0 parts of concentratedhydrochloric acid was heated for about two hours. The reaction mixturewas rendered slightly alkaline by the addition of 50 percent aqueoussodium hydroxide and stored in the refrigerator for two days. Thereaction mixture was (11GB filtered to remove a small amount of solidand the filtrate was acidified with 48 parts of concentratedhydrochloric acid. Acetone was slowly added to the acidified filtrateuntil precipitation started. When precipitation of the product wascomplete, the solid was collected on a filter, washed with acetone, anddried at 75 C. to obtain 8.2 parts of N,N-dimethyl-N-(4nitrophenyl)carbamylmethyl N 3 aminopropylammonium chloride as themono-hydrochloride salt, a white solid which melted at 244245 C.

When theN,N-dimethyl-N-(4-nitrophenyl)carbamylmethyl-'N-3-aminopropylammoniumchloride hydrochloride thus obtained is neutralized with dilute alkaliand then subjected to reduction according to the procedure of 1b above,there is obtained N,N-dimethyl-N-(4-aminophenyl)carbamylmethyl N3-aminopropylamrnonium chloride.

7. N,N-Dimethyl-N- 3-amino 4-methoxybenzyl) -N-3- aminopropylammoniumchloride When N,N-dimethyl-N- 3-amino-4-methoxybenzyl -N-3-formamidopropylammonium chloride obtained in lb or 10 above ishydrolyzed by heating in a dilute aqueous solution of hydrochloric acidaccording to the procedure of 4 above, there is obtained N,N-dimethyl--(3-amino- 4-methoxybenzyl)-N-3 aminopropylammonium chloride as thedihydrochloride salt.

In addition to those for which detailed preparations are given above,the following N-R -N-[(lower-alkylene) -Y NH N R N[*(1ower-alkylene)-NRY] quaternary ammonium intermediates are obtainedwhen the indicated nitrophenyl-substituted quaternizing agent isinteracted with the indicated tertiary amino compound according to aprocedure similar to those given under 1a, 2, 3a, and 5a and theresulting nitro-substituted compound is reduced by a procedure similarto those given under lb or 10:

N,N-Dimethyl-N-2-(3-amino 4 methylphenyl)ethyl-N-3-formamidopropylammmonium chloride starting withN-(3-dimethylaminopropyl)formamide and 2-(4-methyl- 3-nitrophenyl)ethylchloride;

N-Methyl-N-3-(4- aminophenyl)propyl N,N bis(3- formamidopropyl)ammoniumchloride starting with N,N- bis(3-formamidopropyl)methylamine and 3 (4nitrophenyl propyl chloride;

N,N-Diethyl-N-6-(3-amino 4 methoxyphenyl)hexyl-N-3-formamidopropylammonium chloride starting with N-3-diethylaminopropyl formamide and 6- (4-methoxy- 3-nitrophenyl)hexylchloride;

N,N Dimethyl-N-2-ethyl-4-(3-amino-5-chlorophenyl)butyl-N-3-benzamidopropylammonium chloride starting withN-'(3-dimethylaminopropyl)benzamide and 2-ethyl-4-(3-chloro-5-nitrophenyl)butyl chloride;

N,NDimethyl-N-1-methyl-3-(4-amino-3-bromophenyl)propyl-N-3-acetamidopropylarnmoniumchloride starting with N (3 dimethylaminopropyl)acetamide and1-methyl-3- 3-bromo-4-nitrophenyl propyl chloride;

N,N Diethyl-N-3-(4-amino-2-chlorophenylcarbamyl)propyl-N-4-methyl-4-formamidobutylammonium chloride starting withN-(4-diethylamino-1-methylbutyl)formamide and2,4-dichloro-4'-nitrobutyranilide;

N,Ndimethyl-N-(N-methy1-4-amino 2-chlorophenylcarbamyl)methyl N 3phthalamidopropylammonium chloride starting withN-(3-dimethylaminopropyl)phthalamic acid and2,2-dichloro-Nmethyl-4'-nitroacetanilide;

N,N-Bis(2-hydroxyethyl) N(3-amino-4-methoxybenzyl)-N-3-forrnamidopropylammonium chloride startingwith N (3 diethanolaminopropyl)formamide and 4-methoxy-3-nitrobenzylchloride;

1-[2-(3 Amino 4methylphenyl)ethyl]-l-2-formamidoethyl)-4-formylpiperazinium chloridestarting with N [2 -'(4-formylpiperazinoethyl]formamide and 2-(4-methyl-3-nitrophenyl)ethyl chloride;

N-Ethyl-N-l-methylbutyl N [2 (2-ethyl-4-aminophenylcarbamyl)ethyl] N 2propionamidoethylammonium chloride starting withN-[2-(N-ethyl-N-l-rnethyl- The foregoing N-R -N-[ (lower-alkylene) -Y NH]-N- R -N-[(lower-alkylene) NR COR] ammonium halide intermediates are ofcourse, useful for preparing the compounds of Formula VII in which Y isCOR. In addition, they may be hydrolyzed by a procedure similar to thatin C-4 hereinabove to obtain the corresponding N-R -N-[( lower alkylene)Y NH N-R -N-[ (loweralkylene)-NRH]ammonium halide intermediates whichare useful for and afford an alternate method for preparing the finalproducts of Formula VII in which Y is hydrogen.

D. N-R -N-[(Lower Alkylene) -Y -H]-N-R -N-[(Lower-Alkylene -NRY]Quaternary Ammonium Intermediates (Formula XI) 1.N,N-Dimethyl-N-2-(N'-ethylanilino)ethyl-N-3- formamidopropylammoniumchloride A stirred mixture of 157 parts ofN-(3-dimethylaminopropyl)formamide in 20.0 parts of water was heated to80 C. and over a period of one and one half hours there was added 171parts of N-ethyl-N-(2-chloroethyl) aniline. The reaction mixture washeated at 95100 C. until a small sample when diluted with water gave aclear solution. After about seven hours of heating at 95- 100" C. therewas obtained N,N-dimethyl-N-2-(N-ethylanilino)ethyl-N-3formamidopropylammonium chloride in the form of an aqueous solution.

2. N,N-Dimethyl-N-Z- (N-ethylanilino ethyl-N3 aminopropylammoniumchloride Dilute hydrochloric acid hydrolysis of N,N-dimethyl- N 2 (N'ethylanilino)ethyl-N-3formamidopropylammonium chloride following aprocedure similar to that of C-4 above gives N,N-dimethyl-N-2-(N'ethylanilino) ethyl-N-3-aminopropylammonium chloride.

When the indicated tert. amino compound is quaternized with theindicated N-R -N-(halo-lower-alkylene)- substituted aniline oraminonaphthalene according to a procedure similar to that of D1 above,the following N- R -N-[(lower-alky]ene) -Y -H] N R N[(loweralkylene)NRCOR]ammonium halide intermediates are obtained:

N-Ethyl-N-l methylbutyl-N 4 (N-ethylanilino)butyl-N-2-(Npropylpropionamido)ethylammonium chloride fromN-[Z-N-ethyl-N-l-methylbutyl)aminoethyl] propionamide andN-ethyl-N-(4-chlorobutyl)aniline;

N,N-Dimethyl-N-3-ethyl 4 (N-methylanilino)butyl-N-6-iso-butyramidohexylammonium chloride from N-(6-dimethylaminohexyl)iso-butyramide and N-methyl-N-(Z-ethyl-4-chlorobutyl) aniline;

N-6-(N Propylanilino)hexyl N 2-acrylarnidoethylpiperidinium chloridefrom N-(Z-piperidinoethyl)acrylamide andN-n-propyl-N-(6-chlorohexyl)aniline;

N-Z-(N Ethylanilino)ethyl-N3-valeramidopropylpyrrolidinium chloride fromN-(3-pyrrolidinylpropyl)valeramide and N-ethyl-N-(2-chloroethyl)aniline;

N,N-Diallyl N 2,2-dimethyl-3-anilinopropyl-N-2-phenylpropionarnidoethylammonium chloride from N-(2-diallylaminoethyl)phenylpropionamide and N-(2,2-dimethyl-3-chloropropyl)aniline;

l-Benzyl 4 formyl-l-[4-(N-n-butylanilino)-2,3-dimethylbutylJpiperaziniumchloride from l-benzyl-4- formyl piperazine andN-n-butyl-N-(2,3-dimethyl-4-chlorobutyl) aniline;

N,N Diethyl-N-3-(2 naphthylamino)propyl N 3-methyl-3-acrylamidop'ropylammonium chloride from N- (l-methyl3-diethylaminopropyl)acrylamide and N-(3- chloropropyl) 2-naphthylamide;

1 (2 Hydroxyethyl)4-(m-toluoy1)-1-(Z-methyl-N- ethyl-l-naphthylamino)propylpiperazinium chloride from 1 (2hydroxyethyl)-4-(m-toluoyl)piperazine and N-ethyl-N-(2-methyl-3-chloropropyl)-l-naphthylamine;

N,N Bis(2 hydroxyethyl)N--(N-isopentylanilino) pentyl N 2,2dimethyl-Z-phenylacetamidoethylammo- 24 nium chloride from N-(2diethanolamino-l,l-dimethylethyl)phenylacetamide and N isopentylN-(S-chloropentyl)aniline;

N Methyl N-isopropyl-N-S-(N-methyl-l-naphthylamino)pentyl-N3-salicylamidopropylammonium chloride from N[3-(N-isopropyl-N-methyl)aminopropyl] salicylamide andN-methyl-N-(5-chloropentyl) l-naphthylamine;

N Methyl N-3-formamidopropyl-N-2-(N-tert.-butyl- 2 -naphthylamino)ethylN 3-formamidopropylammonium chloride fromN,N-bis(3-forma1nidopropyl)methylamine and NterL-butyl-N-(2-chloroethyl)2-naphthylamine;

N Methyl-N-4-(N-ethylanilino)butyI-N-Z-acetamidoethylN-3acetamidopropylamrnonium chloride from N- [3(N-methyl-N-2-acetamidoethyl)aminopropyl1acetamide andN-ethyl-N-(4-chlorobutyl)-aniline;

N,N Dimethyl-N-4-(N-ethylanilino)butyl-N-S-[N-(3- hydroxypropyl)formamido] propylammonium chloride from N(3-hydroxypropyl)-N-(3-dimethylaminopropyl) formamide andN-ethyl-N-(4-chlorobuty1)aniline;

N Methyl N-3-ethyl-4- (N-methylanilino)butyl-N,N- bis- 3-N-rnethylformamido propyl] ammonium chloride from N,Nbis[3-(N-methylformamido)propyl1methy1- amine and Nmethyl-N-(2-ethyl-4-chlorobutyl)aniline; and

N,N Di-n-propylamino-N-2,2-dimethyl-3-anilinopropyl-N-l methyl2-(N-ethyl-p-nitrobenzamido)ethylammonium bromide fromN-ethyl-N-(2-di-n-propylamino-2- methylethyDp nitrobenzamide andN-(2,2-dimethyl-3- chloropropyl)aniline.

The foregoing N-R -N-[ (lower-alkylene) -Y' -H]-N-R"-N-[(lower-alkylene)NRCOR] ammonium halide intermediates can of course,be used directly to produce the compounds of Formula VIII in which Y isCOR. Additionally, they may be hydrolyzed by a procedure similar to thatdescribed in C4 hereinabove to obtain the corresponding N R-N-[(lower-alkylene) -Y -H]-N-R -N- [(lower-alkylene)NRH]ammonium halideintermediates which are useful for and afford an alternate method forpreparing the final products of Formula VIII in which Y is hydrogen.

E. N-R -N- (Lower-Alkylene)-Y -NH -N-R -N-R Quaternary AmmoniumIntermediates (Formula XII) 1.N-(3-amino-4-methoxybenzyl)-N,N,N-trimethylammonium chloride a) To astirred solution of 35.0 parts of trimethylamine in parts of water therewas added over a one and onehalf hour period 100.8 parts of4-methoxy-3-nitrobenzyl chloride. The reaction mixture was heated atapproximately 50 C. for three and a half hours and was then diluted withan additional 50 parts of water. The solution was allowed to cool toabout 25 C. and the pH was adjusted to 4.9 by the addition of diluteacetic acid. The solution was clarified by filtration and was useddirectly for reduction of the thus obtained N-(3-nitro-4methoxybenzyl)N,N,N-trimethylammonium chloride dissolved therein.

(b) The aqueous solution of N(3-nitro-4-methoxybenzyl)-N,N,N-trimethylammonium chloride obtained in(a) was heated to approximately 85 C. Then parts of iron powder wasadded at a rate sufficient to maintain a temperature in the range 85 -90C. without further external heating. At the end of the addition, heatingwas resumed at 85 -90 C. for one hour and then the reaction was setaside at room temperature overnight. The reaction mixture was heated to80 C. and the pH ad justed to approximately 8.0 by the addition of adilute aqueous solution of sodium carbonate. The mixture was allowed tocool to approximately 45 C. and was then filtered with the aid of 3parts of decolorizing charcoal. A sample of the clear solution wasanalyzed for free amine 25 content by diazotization using a standardizedsodium nitrite solution. The analytical results showed that N-(3- amino4 methoxybenzyl)-N,N,N-trimethylammonium chloride was obtained in nearlyquantitative yield. The product was used directly in the form of itsaqueous solution without isolation.

2. N- 3-amino-4-methoxybenzyl -N- 2-hydroxyethyl N,N-dimethylammoniumchloride (a) A stirred solution of 46.4 parts of dimethylaminoethanol in50 parts of water was heated to 50 C. and over a period of two hoursthere was added 100.8 parts of 4-methoxy-3-nitrobenzyl chloride. Thereaction mixture was heated at 50-55 C. for three hours longer and thenset aside at room temperature overnight. The mixture was filtered andthe clear filtrate containing the product, N(3-nitro-4-methoxybenzyl)-N-(2-hydroxyethyl) N,N'-dimethylammoniumchloride, was used directly for reduction of the nitro group.

(b) A mixture of 150 parts of iron powder, 80 parts of water and 10parts of concentrated hydrochloric acid was stirred vigorously andheated to 90 C. Heating was stopped and 259.1 parts of the aqueoussolution of N- (3nitro-4-methoxybenzyl)-N-(2-hydroxyethyl)-N,N-dimethylammonium chlorideobtained in (a) above was added at a rate suflicient to maintain thetemperature at 8590 C. After the addition was complete, heating at 85-90C. was continued for one hour. Then 6.0 parts of sodium carbonate wasadded and the mixture was cooled to 40 C. and filtered. A sample of thesolution was analyzed for free amine content by diazotization using astandardized sodium nitrite solution. The analytical results showed thatthe solution contained 113.6 parts of the product,N-(3-amino-4-methoxybenzyl)-N-(2- hydroxyethyl) N,N-dimethylammoniumchloride. The product was used directly in the form of its aqueoussolution without isolation.

3. N-(3-amino-4-methoxybenzyl) -N,N-bis(2-hydroxyethyl)-N-methylammoniumchloride (a) A stirred solution of 61.9 parts of N-methyl diethanolaminein 100 parts of water was heated to 50 C. and over a period of one and ahalf hours there was added 201.6 parts of 4-methoxy-3-nitrobenzylchloride. The reaction mixture was heated at 55-60 C. for approximatelysix hours while adding in small amounts a total of 23.1 parts ofN-methyl diethanolamine as needed in order to keep the reaction slightlyalkaline. At the end of the heating period, the reaction mixture wasdiluted with 100 parts of water and was set aside at room temperatureovernight. The next day the resulting slurry was filtered. The solidremoved by filtration was dried to recover 61.2 parts of unreacted4-methoxy-3-nitrobenzyl chloride. The clear filtrate containing theproduct, N-(3- nitro 4 methoxybenzyl)-N,N-bis(2-hydroxyethyl)-N-methylammonium chloride, was used directly for reduction of the nitrogroup.

(b) The aqueous solution ofN-(3-nitro-4-methoxybenzyl)-N,N-bis(2-hydroxyethyl)-N methylammoniumchloride obtained in 3a above was made slightly alkaline by the additionof a small amount of 5 percent aqueous sodium hydroxide. Then 42 partsof sodium acetate were added to the solution and the mixture was heatedto 65 C. Heating was stopped and 210 parts of iron powder were added tothe stirred reaction mixture at a rate such as to maintain thetemperature at 65 70 C. without external heating. At the end of theaddition, heating was resumed at 6S-70 C. for four hours. The reactionmixture was then treated with 7 parts of decolorizing charcoal andfiltered to obtain an amber solution. A sample of the solution wasanalyzed for free amine content by diazotization using a standardizedsodium nitrite solution. The analytical results showed that the solutioncontained 165 parts of N-(3-arnino-4-methoxybenzyl)-N,N bis(2hydroxyethyl)-N-methylammonium chloride. The product was used directlyin the form of its aqueous solution without isolation.

4. N- 3-amino-4-methoxybenzyl)-N-(2-hydroxypropyl)- N,N-dimethylammoniumchloride (a) Proceeding in a manner similar to that described above in1a, 16 parts of 1-dimethylamino-2-propanol and 32 parts of4-methoxy-3-nitrobenzyl chloride were interacted in 14 parts of water toobtain N-(3-nitro-4-methoxybenzyl)-N-(2-hydroxypropyl)-N,Ndimethylammonium chloride. The product was not isolated but was useddirectly in solution for reduction of the nitro group.

(b) Following a procedure similar to that described above in 1b, andusing 33 parts of iron powder and 6 parts of acetic acid, theN-(3-nitro-4-methoxybenzyl)N- (2-hydroxypropyl)-N,N-dimethylammoniumchloride obtained in the form of its aqueous solution from 4a above wasreduced to obtain 39.6 parts ofN-(3-amino-4-methoxybenzyl)-N-(2-hydroxypropyl)-N,N-dimethylaminoniumchloride in the form of an aqueous solution.

In addition to those for which detailed preparations are given above,the following N-R -N-[(lower-alkylene)-Y NH ]-N-R -N-R quaternaryammonium intermediates are obtained when the indicatednitrophenyl-substituted quaternizing agent is interacted with theindicated tertiary amino compound according to a procedure similar tothose given under 1a, 2a and 3a and the resulting nitrosubstitutedcompound is reduced by a procedure similar to those given under 1b, 2band 3b:

N-(4-amino-2-iodobenzyl)-N,N,N-tri n hexylammonium bromide starting withtrihexylamine and 4-nitro-2- iodobenzyl bromide;

N-Methyl-N-n-propyl-N-6-(3-amino-4 butoxyphenyl) hexyl-N-n-hexylammoniumchloride starting with N- rnethyl-N-propylhexylamine and 6-(4-butoxy 3nitrophenyl)hexyl chloride;

N,N-Diethyl-N allyl-N-1-methyl-3- (4-amino-3 bromophenyl)propylammoniumchloride starting with N,Ndi ethylallylamine and1-methyl-3-(3-bromo-4-nitrophenyl) propyl chloride;

N,N-Di-n-butyl-N-3-hydroxypropyl-N-2-(4 arnino 3-n-butylphenyl)ethylammonium bromide starting with 3-di-n-butylamino-l-propanol and 2-(3-n-butyl 4 -nitro phenyl)ethylbromide;

N-Methyl-N-allyl-N-G-n-hydroxyhexyl-N-4-amino 3- fluorobenzylammoniumchloride starting with 6-methylallyl-amino-l-hexanol and3-fluoro-4-nitrobenzyl chloride;

N,N-Di(3-hexenyl)-N-2-hydroxyethyl-N-3 amino 5- ethylbenzylammoniumchloride starting with 2-di(3-hexenyl)aminoethanol and2-ethyl-5-nitrobenzyl chloride;

N-(Z-Butenyl)-N-n-pentyl-N-vinyl-N-l-methyl 3 (4-amino-3-bromophenyl)propylammonium bromide starting withN-2-butenyl-N-vinyl-n-pentylamine and l-methyl 3-(3-bromo-4-nitrophenyl) propyl bromide;

N-n-Propyl-N-Z-hydroxyethyl-N-3 hydroxypropyl N-4-(4-aminophenyl)butylammonium chloride starting with3-(N-n-propyl-N-Z-hydroxyethyl)amino-1 propanol and 4- (4-nitrophenylbutyl chloride;

N,N-Di 2-hydroxyethyl -N-allyl-N-2-ethyl-4- 3-amino-S-chlorophenyl)butylammonium chloride starting with N- allyldiethanolamine and 2-ethyl-4-(3-chloro-5-nitrophenyl)butyl chloride;

N ,N-Di-n-butyl-N-2- hydroxypropyl-N-2-(3 amino 4-methylphenyl)ethylammonium chloride starting with 3-dibutylamino-Z-propanol and 2-(4-methyl-3-nitrophenyl) ethyl chloride;

N-Methyl-N-isobutyl-N-3-hydroxybutyl-N 4 aminobenzylammonium iodidestarting with N-3hydroxybutyl- N-isobutylmethylamine and 4-nitrobenzyliodide;

N-Methyl-N-tert.-butyl-N-methallyl-N-3 amino 4- methoxybenzylammoniumchloride starting with N-methallyl-N-methyl-tert.-butylamine and4-methoxy-3 nitr0- benzyl chloride.

27 PREPARATION OF THE PHTHALOCYANINE DYESTUFFS AND TESTING PROCEDURESExample 1 To a solution containing 180 parts of N-(3-dimethylaminopropyl)formamide in 785 parts of isopropyl alcohol were added 179.4parts of tetrakis(chloromethyl)copper phthalocyanine. The mixture washeated under reflux with constant stirring for 3 hours, after which timethe mixture was allowed to cool and the lumpy solid was removed byfiltration. The filter cake was washed well with isopropyl alcohol. Theresulting highly water-soluble, brilliant turquoise powder was purifiedby dissolving it in water, precipitating the dye with acetone, andcollecting the product by filtration. The filter cake was washed wellwith isopropyl alcohol and was dried at 7580 C. Chemical analysis of theproduct showed that an average of approximately two of the chloromethylgroups reacted to form quaternary ammonium groups and an average ofapproximately two of the chloromethyl groups reacted with the isopropylalcohol solvent to form isopropoxy groups.

Chromaticity data were determined by test procedures outlined below onhandsheets dyed with the dyestuif prepared as above by incorporating thedyestulf with aqueous slurries of paper-pulp in an amount equal to about0.1 percent by weight based upon the weight of dry pulp. These datashowed that the dominant wavelength (shade) of the dyed handsheet was486.4 millimicrons and the excitation purity was 24.2. The tristimulus Yvalue (brightness to the eye) was 63.1.

An aqueous solution containing 0.03 g. of this dyestutf per liter ofsolution had two maxima in the visible absorption spectrum: at 618millimicrons, A=1.27 and at 665 millimicrons, A=0.88.

In the bleach test described below, papers dyed with this dyestutf werefound to be highly bleachable. The dye was found to bleed slightly inthe water-bleed test and in the soap-bleed test.

When the above preparation was repeated using dimethylformamide as thereaction medium, the product again precipitated from the reactionmixture as quaternization proceeded. The resulting product contained anaverage of between two and three quaternary ammonium groups of theformula formula H,NCH,CH;-CH;NHCHo 2-4 01- CIHQ 2-4 The dyestutfprepared in water was somewhat greener in shade than the dyestuffprepared in either isopropyl alcohol or dimethylformamide.

When this reaction is repeated and into the reaction medium isintroduced a quantity of phenol, an amine, for example triethylamine,morpholine, ethanolamine, and dibutylamine, or a hydrazine, for example,hydrazine hydrate, unsymmetrical dimethylhydrazine, andisopropylhydrazine in an amount equivalent to one to two molecularequivalents for each molecular equivalent of phthalocyanine reactant, adyestutf containing an average of from one to two phenoxy, amino, orhydrazino substituents, respectively, is obtained.

Testing procedures The following test procedures were employed todetermine the relative shades of the dyestuffs produced and to determinethe resistance of the dyestuffs to bleed in moist paper, bleed frompaper in the presence of soap, and to bleaching with hypochloritebleach.

Shade Chromaticity values of dominant wavelength and excitation purityare determined by measuring the reflectance tristimulus values of dyedhandsheet paper on a General Electric recording spectrophotometer incombination With a Librascope automatic tristimulus integrator andplotting the points on a chromaticity diagram according to the proceduredescribed by A. C. Hardy, Handbook of Colorimetry, The Technology Press,Massachusetts Institute of Technology, Cambridge, Mass, 1936.

The dominant wavelength is a measure of the shade imparted to the paperby the dye, and the excitation purity is a measure of the saturation ordepth of the color. Inasmuch as the eye is more sensitive to minorvariations in color than the most sensitive instrument, the shadesimparted to test papers were also compared visually.

In some cases absorbance of aqueous solutions in the visible lightregion were measured by standard methods on a Perkin-Elmer Model 4000ASpectracord.

Water Bleed Test This procedure is a modification of the AATCC StandandTest Method 15-1962, Colorfastness to Perspiration.

Test pieces 1% inch in diameter (approximately one square inch area) arecut from the dyed paper to be tested and marked, with lead pencil, toindicate sample and wire (or felt) side. One or more dyed papers ofknown dye migration quality are included in the test series asstandards.

The absorbent material consists of filter paper having at least one sidewith smooth finish (Eaton-Dikeman No. 613, or equivalent) cut to 2 inchby 3 inch rectangles. In addition, smooth, flat, glass or clear plasticplates of adequate stiffness, measuring 2 /2 inches wide and 3 to 4 /2inches long, are required as separating plates. A 500 gram weight servesas a dead weight loading.

Two filter paper absorbent pieces are used for each dyed paper testcircle, one for each side. These are marked on the smoother surface(with lead pencil) prior to beginning the test to indicate the sampleand the sample surface (Wire or felt) which it will contact.

The migration test sandwich is constructed as follows. A separatingplate is placed on a horizontal support and one piece of the filterpaper placed centrally on this plate with the smoother side up. Thecircular dyed paper test piece, held by tweezers, is immersed in waterat room temperature for 3 seconds, drained for 3 seconds, andimmediately centered on the filter paper, making sure that side (wire orfelt) identifications are correct. Immediately, the second piece offilter paper, smoother side downward, is centered on the test circle andfollowed at once by another separating plate. This sandwich is pressedfor a moment with the fingers, after which, with out delay, a piece offilter paper is positioned on the top separating plate as before toreceive a second test circle of wetted dyed paper. The above procedureis then repeated as rapidly as possible and without interruption,stacking one sandwich on the other, until all dyed paper test pieceshave been put under test.

As soon as a stack is completed a 500 gram weight is centered on the topseparating plate, and the assembly 29 shrouded with moisture vaporresistant film to avoid undue drying. The stack is allowed to stand atroom temperature for 4 hours, during which time ambient temperatures areoccassionally recorded.

At the end of the migration period the stack is disassembled, and eachdyed paper test circle and its two filter paper absorbents clipped to asupporting card. A separate card is used for each test circle. The dyedpaper test circles and filter papers are air dried at room temperaturefor at least two hours before ranking. Relative degrees of dyemigration, as compared to that from standard samples, are determined byvisual ratings, under Macbeth Northlight, of the intensity of dye stainon the filter paper surface which had been in contact with the testcircle. Migration from the wire and felt sides are ranked separately.

Soap Bleed Test This test compares the degree to which dyed papers willdiscolor a soap solution in which the paper is immersed.

A stock supply of soap solution containing 0.5% soap by weight isprepared by adding neutral white soap flakes (a mixture of 80 percentsodium soap and percent potassium soap produced from 70 percent tallowand percent coconut oil glyceride blend; Ivory brand, Proctor and GambleCo.) slowly with stirring to hot tap Water and then heated further withoccasional stirring to 7075 C.

Portions of 400 ml. of this solution are measured into 1,000 ml. beakers(one beaker for each test), covered with a watch glass, and allowed tocool to 60-65 C. At this point approximately 1.5 grams of the dyed paper(one half of a 3.0 gram, 8 inch square handsheet) is crumpled andimmersed in its soap test solution.

Soaking is allowed to continue for 20 to 24 hours, with gradual coolingto room temperature. During this period the paper is squeezed by handwhile submerged (or stirred vigorously with a glass rod) on at leastthree occasions during the first five hours, and again about one hourbefore ending the test period.

At the end of the immersion period the beaker contents are stirred andenough immediately screened through a double screen of 100 meshstainless steel screening to nearly fill a two ounce, square clear glassbottle, which is then capped. These filtrates are then visually ratedfor color intensity under laboratory ceiling fluorescent tube lights.

Bleach Test This procedure compares the degree to which the color ofdyed or shade papers would be discharged in a waste paper recoveryoperation employing hypochlorite bleach.

Test pieces measuring inch by 1 /2 inch are die cut from the papers tobe compared and identified, using lead pencil markings.

A stock supply of hypochlorite bleach is prepared by diluting commercialhypochlorite bleach (nominal available chlorine content, 5.0%) withdistilled water to a concentration of 0.09 grams available chlorine per100 ml. solution. Before diluting this solution to final volume the pHis adjusted with dilute sulfuric acid to pH 4.0 to 4.5.

Portions of 20 ml. each of the hypochlorite stock solution, at roomtemperature, are measured into test tubes 1 inch in diameter and 7 to 8inches long, one tube for each test specimen. An extra such tube isprepared, fitted with a thermometer extending into the bleach solution,to follow the rise in bleach temperature.

One paper test piece is then dropped into each tube and submerged in thebleach liquor, adding all pieces as quickly as possible. The tubes areimmediately stoppered and all simultaneously placed in a water bathpreviously heated to 54 to 56 C. (129 to 133 F.).

The test pieces are observed, especially during the very early minutesof bleaching, for obvious difierences in the rate of color discharge.The temperature of the bleach liquors rises rapidly during the first 5minutes.

While maintaining the water bath temperature in the 54 to 56 C. range,the bleach tubes remain, without agitation of the test pieces, in thewater bath for 30 minutes. Occasional readings of the temperature of theblank bleach tube during this period are recorded.

At the end of this time all tubes are removed from the water bath,immediately filled with cold tap Water, and the test pieces rinsed asquickly as possible, with cold tap water, into a large Buchner funnel(with no filter paper disk) where they are thoroughly washed withrunning cold tap water. The washed test pieces are finally placed on ablotter and air dried at room temperature.

The relative degree of bleaching is judged by visually ranking, underMacbeth Northlight, the intensity of residual color in the dry testpieces.

Example 2 An aqueous solution of copper phthalocyaninebis(isopropoxymethyl) bis(methylene S-formamidopropyl dimethylammoniumchloride) prepared in isopropyl alcohol as described in Example 1B from89.4 parts of tetrakis (colormethyl)copper phthalocyanine and 21.2 partsof N- (3 dimethylaminopropyl)formamide was heated in 75 parts of watercontaining 12 parts of concentrated hydrochloric acid for about twohours. The reaction mixture was then neutralized with 50 percent aqueoussodium hydroxide. A portion of this solution was filtered throughdiatomaceous earth, and isopropyl alcohol was slowly added to thefiltrate until precipitation just started. When precipitation of theproduct was complete, the solid was collected on a filter, washed withisopropyl alcohol, and dried at C. Elemental analysis of this productshowed that it consisted of a mixture of copper phthalocyaninessubstituted by an average of approximately two moieties andapproximately two isopropoxymethyl moieties.

Chromaticity data based on the spectral reflectance of paper handsheetsprepared as described above showed a dominant wavelength of 486.6millimicrons (slightly greener than the formamide derivative ofExample 1) and an excitation purity of 24.4. The tristimulus Y value ofbrightness was 62.6.

In the bleach test, this dye was found to have excellent bleachabilityproperties not significantly different from the formyl-substituteddyestuff described in Example 1. However, compared to saidformyl-substituted dyestutf, this dyestuff showed significantly superiorresistance to bleed in both the water bleed and the soap bleed tests.

Example 3 Seven parts of tetrakis(chloromethyl)copper phthalocyanine and12 parts of N-(3-dimethylaminopropyl)formamide were refluxed in 32 partsof dry methanol for three hours. The reaction mixture was then cooledand filtered through diatomaceous earth. The filtrate was poured into400 ml. of isopropyl alcohol and the precipitate was collected on afilter, washed well with isopropyl alcohol, and dried. Elementalanalysis showed that this product was essentially thetetrakis(quaternary ammonium) compound of the formula L CH3 The dyestuflwas highly water-soluble and imparted a brilliant turquoise color topaper.

The visible absorption spectrum of an aqueous solution of this dycstulTcontaining 0.03 g. of dye per liter of solu- 31 tion had two maxima: at626 millimicrons, A=1.14; at 672 millimicrons, A: 1.375.

Hydrolysis of the above product according to the procedure described inExample 2 yields the compound copper phthalocyanine tetrakis(methylenedimethyl 3-aminopropylammonium chloride) of the formula When thisreaction is carried out using tetrakis(chloromethyl)phthalocyanine(unmetallized) the corresponding unmetallized water-solubletetrakis(quaternary ammonium)phthalocyanine dyestuff is obtained.

Example 4 L CHg-CH:

The visible absorption spectrum of an aqueous solution of this dyestuff,containing 0.03 g. of dye per liter of solution, showed two maxima: at614 millimicrons, A=1.16; at 670 millimicrons, A=O.68.

Hydrolysis of the above-mentioned formamide compound according to themethod described in Example 2 yielded a mixture of copperphthalocyanines substituted with from two to four (methylene4-methylpiperazinium chloride) radicals, and having the formula P c L CH-CH3 TECHZCIJH The visible absorption spectrum of an aqueous solution ofthis dyestuif, containing 1.5 g. of dye per liter of solution, showedtwo maxima: at 613 millimicrons, A=1.35; at 670 millimicrons, A=0.69.

Example 5 Following the procedure given in Example 1, tetrakis(chloromethyl)copper phthalocyanine was refluxed in isopropyl alcoholwith six molecular equivalents of N-(S-dimethylaminopropyl)acetamide forthree hours. When cool, the reaction mixture was poured into acetone toprecipitate the partially-soluble product, which was then collected on afilter and washed well with acetone. The resulting product, consistingprimarily of a dyestutf of the formula I" CHa was a brilliant bluepowder which was readily soluble in water, leaving no residue.

The visible absorption spectrum of an aqueous solution of this dyestuffcontaining 0.04 g. of dye per liter of solution showed two maxima: at620 millimicrons, A=1.4; and at 668 millimicrons, A=1.22.

Chromaticity values of paper handsheets prepared as described in Example1 showed that the dominant wavelength was 986.6 millimicrons and theexcitation purity was 24.0. The tristimulus Y value of brightness was63.7.

No significant dilference was found on the bleachability of paper dyedwith this dyestufi in comparison with the dyestuffs described inExamples 1 and 2. In the soap bleed test, this dyestuif showed somewhatless resistance to bleed than did the dyestutf of Example 1.

Example 6 moieties and with 0 to 2 chloromethyl moieties.

The visible absorption spectrum of an aqueous solution of this dyestuff,containing 0.03 g. of dye per liter of solution showed two maxima: at619 millimicrons, A=1.04; at 670 millimicrons, A=0.705.

Hydrolysis of the above-mentioned formamide compound according to themethod described in Example 2 yielded a mixture of copperphthalocyanines having the formula TECHzC11H The visible absorptionspectrum of an aqueous solution of this dyestuif, containing 0.75 g. ofdye per liter of solution showed two maxima: at 624 millimicrons,A=1.262; at 671 millimicrons, A: 1.08.

Example 7 Following the procedure given in Example I, a mixture oftetrakis(chloromethyl)copper phthalocyanine and six molecularequivalents of N-(3-diethylaminopropyl) formamide in acetonitrile washeated at reflux for 14 hours. The mixture was allowed to cool, and theprecipitated product was collected on a filter. After drying there wasobtained a mixture of copper phthalocyanines substituted with from twoto four moieties and from O to 2 chloromethyl moieties.

The visible absorption spectrum of an aqueous solution of this dyestutf,containing 0.03 g. of dye per liter of solution showed two maxima: at615 millimicrons, A=1.09; at 670 millimicrons, A=0.64.

Hydrolysis of the above-mentioned formamide compound according to themethod described in Example 2 yielded a mixture of copperphthalocyanines having the The visible absorption spectrum of an aqueoussolution of this dyestufif, containing 0.75 g. of dye per liter ofsolution, showed two maxima: at 618 millimicrons, A=1.l6; at 670millimicrons, A=0.72.

Example 8 Proceeding in a manner similar to that described above inExample 1, a mixture of tetrakis(chloromethyl)copper phthalocyanine andsix molecular equivalents of N,N- bis(3-formamidopropyl)methylamino inacetonitrile was heated at reflux for four hours. The mixture wasallowed to cool and the coagulated product was collected on a filter,and washed with isopropyl alcohol. The product was dried at 90 C. invacuo to obtain a product consisting primarily of a dyestuflf of theformula which was a water-soluble blue powder.

The visible absorption spectrum of an aqueous solution of this dyestuficontaining 0.04 g. of dye per liter of solution showed two maxima: at612 millimicrons, A=l.292; and at 668 millimicrons, A: 1.22.

Hydrolysis of this formamide compound following a procedure similar tothat described in Example 2, yielded a product consisting primarily of adyestutf of the formula ECH: 0112 The visible absorption spectrum of anaqueous solution of this dyestufl, containing 0.75 g. of dye per literof solution, showed two maxima: at 625 millimicrons, A=1.218; at 671millimicrons, A=1.00.

Example 9 A .mixture of 32.7 parts of tetrakis(chloromethyl)- copperphthalocyanine, 11.9 parts of N-(3-dimethylaminopropyl)formamide, and125 parts of isopropyl alcohol was stirred and heated at 75-80 C. for 45minutes. To the 1 mixture there was added 5.2 parts of1,1-dimethylhydrazine and heating was continued for two hours. Themixture was allowed to cool and the solid was removed by filtration,washed with isopropyl alcohol and dried at 85 C. The resulting product,consisting primarily of a dyestufl of the formulaCHr-liI-CHz-CHz-CHz-NHC 0 r CHa-N-NHz] 5H3 2 was a blue solid which wasreadily soluble in water.

The visible absorption spectrum of an aqueous solution of this dyestulfcontaining 0.02 g. of dye per liter of solution showed two maxima: at625 millimicrons, A=0.887; and at 670 millimicrons, A=0.68.

Example 10 When a procedure similar to that described in Example 1 isfollowed for the condensation of N-[Z-(N-ethyl-N-1-methylbutyl)aminoethyl1propionamide with bromomethyl copperphthalocyanine, the product obtained is the copper phthalocyaninedyestufi having a single group of the formula *-CH2N-CH2CH2NHCOCH2CH3CH-(CH2)2CH: 6H. Hydrolysis of the above-mentioned carboxylic acylaminocompound according to the method described in ethyl)formamide to obtainthe copper phthalocyanine dyestuff having from one to four groups of theformula CH3 |:cHr-1 ICH2-oH-NHoH0]o1- The visible absorption spectrum ofan aqueous solution of this dyestuff containing 0.03 g. of dye per literof solution, showed a maximum at 618 millimicrons, A=l.235.

Hydrolysis of the above-mentioned carboxylic acylamino compoundaccording to the method described in Example 2 yielded the copperphthalocyanine dyestufi' having from one to four groups of the formulaThe visible absorption spectrum of an aqueous solution of this dyestutf,containing 0.75 g. of dye per liter of solution showed two maxima: at623 millimicrons, A=1.44; at 670 millimicrons, A=0.98.

Example 12 When a procedure similar to that described in Example 1 isfollowed for the condensation of N- (6 dimethylaminohexyl)isobutyramidewith bis(bromomethyl)cobalt phthalocyanine the product obtained is thecobalt phthalocyanime dyestuif having one or two groups of the formulaHydrolysis of the above-mentioned carboxylic acylamino compoundaccording to the method described in Example 2 yields the cobaltphthalocyanine dyestuif having one or two groups of the formula Example13 Following a procedudre similar to that employed in Example 1hereinabove, tetrakis(chloromethyl)copper phthalocyanine was condensedwith N-[2-(4-formylpiper- 35 azinoethyl)formamide to obtain the copperphthalocyanine dyestulf having from one to four groups of the formula ICHO The visible absorption spectrum of an aqueous solution of thisdyestutf, containing 0.03 g. of dye per liter of solution, showed twomaxima: at 614 millimicrons, A=1.16; at 670 millimicrons, A=0.68.

Hydrolysis of the above-mentioned carboxylic acylamino compoundaccording to the method described in 'Example 2 yielded the copperphthalocyanine dyestulf having from one to four groups of the formulaThe visible absorption spectrum of an aqueous solution of this dyestuif,containing 1.5 g. of dye per liter of solution, showed two maxima: at613 millimicrons, A=l.35; at 670 millimicrons, A=0.-69.

Example 14 When a procedure similar to that described in Example 1 isfollowed for the condensation of N-(Z-piperidinoethyl)acryl-amide withtris(bromomethyl)nickel phthalocyanine, the product obtained is thenickel phthalocyanine dyestuff having from one to three groups of theformula CH1 CH1 Br CH3 CH2 Hydrolysis of the above-mentioned carboxylicacylamino compound according to the method described in Example 2 yieldsthe nickel phthalocyanine dyestuff having from one to three groups ofthe formula Example Following a procedure similar to that employed inExample 1 hereinabove, tetrakis(chloromethyl)copper phthalocyanine wascondensed with N-(3-diethanolaminopropyl)formamide to obtain the copperphthalocyanine dyestuff having from one to four groups of the formulaHydrolysis of the above-mentioned carboxylic acylamino compoundaccording to the method described in Example 2 yields the copperphthalocyanine dyestulf having from one to four groups of the formulaHydrolysis of the above-mentioned carboxylic acylamino compoundaccording to the method described in Example 2 yields the ironphthalocyanine dyestuff having from one to four groups of the formulaExample 17 When a procedure similar to that described in Example 1 isfollowed for the condensation ofN-(1-methyl-3-diethylaminopropyl)acrylamide withpentakis(bromomethyl)zinc phthalocyanine, the product obtained is thezinc phthalocyanine dyestulf having from one to five groups of theformula Hydrolysis of the above-mentioned carboxylic acylamino compoundaccording to the method described in Example 2 yields the zincphthalocyanine dyestulf having from one to five groups of the formula AExample 18 Following a procedure similar to that employed in Example 1hereinabove, tetrakis(chloromethyl)copper phthalocyanine was condensedwith N-(3-dimethylaminopropyl)benzamide to obtain the copperphthalocyanine dyestutf having from one to four groups of the formulaThe visible absorption spectrum of an aqueous solution of this dyestuif,containing 0.1 g. of dye per liter of solution showed two maxima: at 607millimicrons, A=0.65; at 680 millimicrons, A'=1.105.

Hydrolysis of the above-mentioned carboxylic acylamino compoundaccording to the method described in Example 2 yields the copperphthalocyanine dyestulf having from one to four groups of the formulaExample 19 When a procedure similar to that described in Example 1 isfollowed for the condensation of l-ethyl-4-propionyl piperazine withtetrachloro-tetrakis(chloromethyl)copper phthalocyanine, the productobtained is the. tctrac loro substituted copper phthalocyanine dyestufihaving from one to four groups of the formula N C O Clix-CH3 CHz-CHzHydrolysis of the above-mentioned carboxylic acylamino compoundaccording to the method described in Example 2 yields thetetrachloro-substituted copper phthalocyanine dyestulf having from oneto four groups of the formula CzH --C Hz-N 01- Example 20 When aprocedure similar to that described in Example 1 is followed for thecondensation of N-(Z-diethanolamino 1,1 dimethylethyl)phenylacetamidewith tetraphenyl-tetrakis(bromomethyl) copper phthalocyanine, theproduct obtained is the tetraphenyl-substituted copper phthalocyaninedyestuif having from one to four groups of the formula Hydrolysis of theabove-mentioned carboxylic acylamino compound according to the methoddescribed in Example 2 yields the tetraphenyl-substituted copperphthalocyanine dyestutf having from one to four groups of the formulaExample 21 Following a procedure similar to that employed in Example 1hereinabove, tetrakis(chloromethyl)copper phthalocyanine was condensedwith N-(3-dimethylaminopropyl)phthalamic acid to obtain the copperphthalocyanine dyestutf having from one to four groups of the formulaCH3 Ha-N-CHr-CHrCHr-NH: Cl-

38 Example 22 When a procedure similar to that described in Example 1 isfollowed for the condensation of l-(2-hydroxyethyl)-4-(mtoluoyl)piperazine with pentakis(chloromethyl)copper phthalocyanine, theproduct obtained is the copper phthalocyanine dyestuft having from oneto five groups of the formula F-CH: CHz-N NOO- Cl- CHr-CH:

CH3 C2H2 H Hydrolysis of the above-mentioned carboxylic acylaminocompound according to the method described in Example 2 yields thecopper phthalocynanine dyestuif having from one to five groups of theformula Example 23 When a procedure similar to that described in Example1 is followed for the condensation ofN-(2-dihexylaminoethyl)n-caproamide with tris(chloromethyl)copperphthalocyanine, the product obtained is the copper phtha1- ocyaninedyestuif having from one to three groups of the formula Hydrolysis ofthe above-mentioned carboxylic acylamine compound according to themethod described in Example 2 yields the copper phthalocyanine dyestuffhaving from one to three groups of the formula Example 24 When aprocedure similar to that described in Example 1 is followed for thecondensation of N-[3-(N-methyl N 2 acetamidoethyl)aminopropyl]acetamidewith bromomethyl copper phthalocyanine the product obtained is thecopper phthalocyanine dyestuff having a single group of the formula CH4- [-CHr-N-CHr-CHrCHz-NHCO-CH: Br-

CHz-CI-Iz-NHCO-CH:

Hydrolysis of the above-mentioned carboxylic acylamino compoundaccording to the method described in Example 2 yields the copperphthalocyanine dyestuif having a single group of the formula When theprocedure outlined in the foregoing Examples is followed for thecondensation of tetrakis(chloromethyl)copper phthalocyanine with thefollowing compounds, there is obtained a copper phthalocyanine dyestuffhaving from one to four of the indicated substituents.

Reactant Substituent in dyestufi productN-methyl-N-(3-pyrrolidinylpropyl)valeramideN-(3-hydroxypropyl)-N-(3-dimethylaminopropy1) formamideN,N-bis[3-(N-methylformamido) propyHmethylamineN-ethyl-N-(Z-di-n-propylamino-2-methylethyl)-p-nitrobenzamideN-n-hexy1-N-[2-(N-ethy1-Nmethy1) aminoethyflpropionamide When theprocedure outlined in the foregoing Examples is followed for thecondensation of tetrakis(chloromethyl)copper phthalocyanine with thefollowing compounds and the acylamino moiety is hydrolyzed ashereinbefore described, there is obtained a copper phthalocyaninedyestuff having from one to four of the indicated substituents:

Reaetant Substituent in dyestufi productN-methyl-N-[2-(Nethyl-N-methyl)arninoethylIpropionamidoN-(3-hydroxypropyl)-N-(3-dimethy1aminopropyl)Iormamide -CH2lICH2-CHzOHz-NH C1- (3H1 N-isopropyl-N-(Z-piperldinoethyl)acrylamideI'CQHI CHz-NGH2CHz-NH Cl HaC CHa 11 0 ()H;

C l l'a'l N-[3-(N-methylacetamido)propyll-N-[2-(N-methylacetamido)ethyl1methyl- CH. OH;

PREPARATION OF THE AROMATIC AZO DYESTUFFS Example 25 In a separatecontainer, 13.4 parts of N,N-diacetoacetp-phenylenediamine, was mixedwith sufficient 2-ethoxy ethanol to form a paste. The paste was slurriedin 300 70 parts of water at 70 C. and to the slurry there was added withstirring 6.0 parts of a 50 percent aqueous solution of sodium hydroxide.A solution resulted which was then added in a thin stream to the colddiazonium solution. The reaction mixture was stirred for four hours at20 C.

75 and then the resulting clear yellow solution was evapo-

1. A QUATERNARY AMMONIUM SALT OF THE FORMULA